Treatment of textile materials



Patented May 30, 1944 TREATMENT OF TEXTILE MATERIALS Gustav Widmer, Basel, and wmi Fisch, nmningen, Switzerland, asslgnors, by mesne assignments, to Ciba Products Corporation, Do-

yer, Del.

No Drawing. Original application June 9, 1937,

Divided and this applicationNovember 20, 1939, Serial No. 305,396. In Switzerland June 27, 1936 Z'Claims. (Cl. 260-72) Serial No. 147,384.

This application is a division of our application Serial No. 147,384, filed in U. S. A. on June 9, 1937 (now U. S. Patent No. 2,191,362, issued Feb. 20, 1940), and in Switzerland on June 27. 1936, and July 20. 1936.

This invention consists in a process of treating textile fibres with the aid of condensation products capable of being hardened from aldehydes and aminotriazines. The process may be used for the purpose, among others, of making dressings fast to washing, for example stiffening dressings;

' of being hardened, for instance phenol resins or carbamide resins, for the purpose of producing a dressing fast to washing or for rendering the fabric impermeable or for fixing a dressing or filling agent or for producing non-creasing properties.

The known processes, however, have the disadvantage that for fixing the artificialv resin or for fixing the dressing or filling agent by means of the artificial resin a separate hardening operation is necessary in which the hardening is accelerated on the one hand by a temperature of substantially above 100 C. and on the other hand by a hardening catalyst, especially one of an acid nature which at the temperature which has to be used is always liable to damage the fibre.

In the copending application Ser. No. 68,355,

filed March 11, 1936, there is described the use of such condensation products for improving textiles, especially for dressing and for diminishing the tendency to creasing. The-process described, however, corresponds in so far with that generally used in the case of the resins capable of being hardened, such as the urea resins and phenol resins, as the process of said specification also requires a heat treatment of the impregnated fiber at temperatures substantially above 100' C. for the purpose of hardening the condensation product. a

The present invention is based on the observation that condensation products capable of being hardened and derived from aminotriazines and aldehydes are suitable in themselves or with the aid of a dressing or filling agent or some other addition for fixing on the fibre even at substantially lower temperatures and with the usual aux-. iliary apparatus without a separate hardening operation. For example, a web of fabric which has been treated with a condensation product and if necessary an addition may be dried and hardened by passage between rollers heated with low pressure steam, viz. at temperatures of about 100 0., whereas when a high temperature is required for the hardening process (in the case of urea or phenol formaldehyde condensation products) the operation requires the use of rollers heated by high pressure steam or electrically. Also temperatures between 50 to C. or even lower temperatures as used in the drying chambers produce satisfactory results. tion may be performed even at room temperature.

Indeed the reac- Especially suitable are condensation products capable of being hardened from aminotriazines and formaldehyde. be named 2:4:6-triamino-1:325-triazine (melamine) -or deaminated products thereof, for instance melam; also 2-chioro-4:6-diamino-1:3:5- triazine (chloromelamine), 2-oxy-4z6-diamino- 1:3:5-triazine (ammeline). However, aldehyde condensation products from other aminotriazines may be used with advantage.

When used asimpregnating or fixing agents the condensation products are preferably dissolved in acidified water or an acid. Suitable acids are inorganic acids, such as hydrochloric acid or phosphoric acid and organic acids such as formic acid, acetic acid, lactic acid, .tartaric acid. Weak and even volatile acids may also be used which,

apart from the fact that the process is conducted at a low temperature, is a great advantage in respect of properties of the fiber. Instead of free acids also acid yielding substances such as for instance ammonium salts, dibromo-cinnamic acid and so on may be used. In all these cases either from the beginning or during the drying and/or hardening step a pH below 7 is produced.

The fiber may also be treated with a neutral or alkaline solution of the condensation product, if desired in the presence of the additional material to be fixed, and the fiber thus treated may be then subjected to the action of acid, for instance bydpassage through an atmosphere containing ac1 The triazine formaldehyde condensation product may be used in various stages of condensation for impregnating the materai, for example it may be in the stage of condensation in which it is soluble without limit in water or in the stage Among aminotriazines may water h in which1the solubility in water is limited, or in the hy 'ophobe stage in which solubility in disappeared and solubility in acid appears. The condensation may also be combined with the impregnation by making an impregnat ing bath of triazi'ne, formaldehyde and an acid condensing agent and any desired addition and impregnating the textile fiber with this bath and drying in ordinary manner. Finally, the fiber may alternatively be'impregnated with a solution of the triazine, advantageously in the form of a water-soluble salt, if necessaryin the presence of an addition, and then after-treated with formaldehyde in the form of vapor. In the last case the whole condensation is efiected on the fiber.

The process is applicable in printing, that is to say for producing local eflects on fabrics, for instance by imprinting a printing paste containing the condensation product and if desired an acid and/or other addition, such as a dressing or filling agent, and if necessary in the presence of a thickening agent. Alternatively the fabric may be locally treated with a neutral or alkaline condensation product, this latter being then fixed by acid. So'also to a fabric which has been pre-treated with a neutral or alkaline dressing mixture containing a condensation product, a dressing or filling agent may be applied, then a fixed acid as the usual thickening and in this mannerthe local hardening efiect produced. In

analogous manner the process may be varied in many ways with or without one or other of the aforesaid additions.

It is also possible to obtain calendering efiects which differ from those obtainable by means of the known resins in that they are much more easily produced, since the hardening occursat a lower temperature, so that no separate harden-' ing apparatus is necessary. Moreover, the effects are of good fastness to washing as compared with those produced by the known artificial resins. I

Textile fibres which, are suitable for treatment by theinvention are native, regenerated and esterified cellulose, for instance cotton, ramie, linen, hemp, sisal, Jute, coconut fiber, artificial silk, also wool, silk or the like, whether dyed or undyed. 1

stiffening dressings cit-filling agents for the fixing of which the invention isparticularlysuitable are, for example, gum arabic, tragacanth, carob bean meal, kaolin, tallow or mixtures of these products.

Softening agents useful for the invention are. for example, fats, such as olive oil, castor oil; glycerine, hydrocarbons, such as paraflln; quaternary ammonium salts which contain an aliphatic residue having more than 8 carbon atoms, for- 'example, thetrimethylammonium sulfate of mono-stearyl-para-phenylenedlamine.

Water-repelling additions suitable for the in-- vention are, for" example, parafiin. wax, resins, aluminium salts, alkaline earth salts, for instance lime soaps, either singly or intermixed with each,

other.

The following examples illustrate the invention, the parts being by weight; parts by volume have the same relation to parts by weight as the litre has to the kilo:

Example 1 Bleached and mercerized cotton satin is i pregnated with a solution which contains in the drying, but for the 1000 parts by volume 120 parts by weight of condensation product (obtained by condensing for about hour 630 parts of 2:4:6-triamino-1g3z5- trlazine (melamine) with 1410 parts by volume of partially neutralized formaldehyde of 32 per cent. strength by volume'at about 80 0., then neutralizing the solution, filtering and drying the filtrate) and 50 parts by volume of formic acid of 86 per cent. strength. The fabric is squeezed between pressure rollers until its weight is 200 per cent. of its dry weight. It is then dried in the usual manner, for instance on a tentering frame. No application of heat is necessary for purpose of accelerating it warm air at 50-60" C. may be used. The feel of the fabric is stiffer and fuller than that of the fabric which has not been treated. By washing for hour at 90 C. with a sol tion containing 5 parts of soap per 1000 parts by volume, the dressing is not substantially effected.

The fabric treated asabove is wetted with difficulty by water drops. This water-repelling effeet is not removed by the soap treatment de scribed above.

The proportion of the condensation product may be so small that no noticeable stiffening is produced. Even with less than grams of condensation product per litre of bath a diminution of the swelling capacity is obtained associated with an increase of fastness to water. In

the case of artificial silk there is also obtained an increase ,of wet tenacity.

' Example 2 of formic acid of 86 per cent. strength and made up to 100 parts by volume of water. With this solution a cotton fabric is impregnated, then squeezed to 200 per cent. of the dry weight and dried in the usual manner on a tentering frame.

By this treatment there is obtained a good stiff finish fast to washing and similar to that described in Example 1.

Example 3 A hydrophobe condensation product is made as follows: 630 parts of 2:4:6-triamino-1:3:5- triazine are condensed at about 80 C. with 1410 parts by volume of neutralized formaldehyde of 32 per cent. strength until a, cooled sample shows a precipitate when diluted with half its volume of water. The solution is then dried at a low temperature. The dry product forms a solution with about 0.6 part by volume of water, whereas more water produces a precipitate.

A colored cotton fabric is impregnated under the conditions described in Example 1 with an aqueous solution containing per 1000 parts by volume 100 parts of the above condensation product and 40 parts of.formic acid of 86 per cent. strength. A fabric dried in the air at room temperature has a strong stifl finish of good fastness ing agents.

using instead of the condensation product described above still soluble in a little water a product of the same composition which, however, has

been so much further condensed that it has become whollyinsoluble in water.

An aqueous solution containing per 1000 parts by volume 100 parts by weight of such a strongly hydrophobic condensation product, 80 parts by volume of formic acid of 86 per cent. strength or 200 parts of the condensation product and 160 parts of formic acid of 86 per cent. strength yields, when used in the manner described in this example, strong stiffening effects of remarkable fastness to washing.

Example 4 -ylenediamine.

The fabric is pressed between rollers untilit is 200 per cent. of its dry weight and then dried on the tentering frame. The drying may be at ordinary temperature but for accelerating it the temperature may be raised to 50-60 C.. The fabric has a very good resistance to creasing, which property is stable to hot soaping.

Example A cotton fabric is impregnated with an aqueous solution containing per 1000 parts byv volume 100 parts of the condensation product made as described in Example 1, 50 parts by volume of I formic acid of 86 per cent. strength, 50 parts of an emulsion of paraffin of per cent. strength containing glue, for example, as the emulsifier.

The fabric is then squeezed between rollers until its weight is 200 per cent. of the dry weight and dried with the aid of a drying apparatus usual in the textile industry, that is to say on a tentering frame or with the aid of drying cylinders. By this treatment the fabric acquires strong water-repelling andwater-proofing properties. After it has been washed with a liquor containing 5 grams of soap per litre at 90 C. for /2 hour the fabric still retains the greater part of its water-proof character.

A similar result is attained by substituting for the pure parailln emulsionan emulsion containing besides the paraffin an aluminium salt, for

instance aluminium acetate; also by impregnating with an aluminium salt in combination with the aminotriazine formaldehyde condensation product there is obtained a good water-repellent effect fast to washing, whereas with the aluminium salt alone the effect'is lost on washing.

The use of aminotriazine formaldehyde condensation products for making water-proof finishes not only improves the water-proof character of th impregnated fabrics but at the same time produces a full, firm feel. The degree of feel of the fabric may be varied by addition of soften- Example 6 10 parts of the dry condensation product obtained as described in Example 1 are dissolved in a mixture of 90 parts by volume of water and 10 parts by volume of formic acid of 86 per cent.

of potato starch with 900 parts by volume of, water and subsequently cooling; the whole is thoroughly mixed.

A cotton fabric of medium weight is saturated with this mixture in a finishing machine, squeezed and then dried on the tentering frame at 22 C.. For accelerating the drying air at a temperature of -60 C. may be used.

By this treatment the starch finish is fixed fast to washing. Even after washing 6 times at 90 C. with a solution containing 5 grams of soap and 2 grams of sodium carbonate per litre the finish remains in the fabric in greater part.

That an optimum fixation is produced by merely drying at room temperature may be proved by the following thermal treatment applied subsequently to the drying at 22 0.:

10 minutes at 70 C. or /2 minute at 100 C. or /2 minute at 140 C. or 4 minutes at 140 C.

The fabric thus after-treated in no case shows an improvement in the fastness to washing.

A similar result is obtained if, for example, the

10 parts by volume of formic acid of 86 per cent. strength used for dissolving the condensation product are exchanged for 10 parts by volume of concentrated hydrochloric acid or 7.5 parts by volume of formic acid of 86 per cent. strength or 20 parts by volume of acetic acid of 80 per cent. strength or 20 parts by volume of lactic acid of 92 per cent. strength or 10 parts of tartaric acid. Moreover, a similar result to that obtained in this example is produced when the 80 parts of potato starch are exchanged for an equal quantity of wheat starch.

An excellent fastness to washing of the fixing effect is obtained if the 10 parts of the condensation product made as described in Example 1 are exchanged for an equal quantity of the strongly hydrophobe condensation product described in the last paragraph of Example 3.

Example 7 A solution of 10 parts of the condensation product made as indicated in Example 1 in a mixture of 90 parts by volume of water and 10 parts by volume of formic acid of 86 per cent. strength is thoroughly mixed with a starch paste containing in 900 parts by volume of water, parts of potato starch and 160 parts of kaolin. A fabric is treated with this mixture as described in Example 6. In this case also the drying follows at ordinary temperature. Washing tests show surprisingly that the filling material. kaolin, and also the stiffening agent itself are not removed after 6 washings conducted as described in Example 6. The intended filling of the fibers of the fabric is clearly notable in th opacity of the fabric to light.

Example 8 A solution of 10 parts of the condensation product made as indicated in Example 1 in a mixture of parts by volume of water and 10 parts by volume of formic acid of 86 per cent. strength is added to a .solution of 80 parts of gum arabic in 1000 parts by volume of water. With this so-' lution a cotton fabric printed in color is saturated as described in Example 6. The excess of liquor is squeezed out by rollers and the fabric is then dried at 34 C. on the tentering frame.

The fabric thus treated even after many washings shows a full grip and a medium stiffness;

the dressing itself is inconspicuous.

Similar results are obtained when in this "e ample 80 parts oi gum arabic are exchanged for 70 parts of carob bean flour or 60 parts of tragacanth.

Example 9 tic soda solution, filteringand dryingthe residue,

are dissolved in 70-parts by volume of formic acid of 86. per cent. strength, and this solution is thoroughly mixed with 700 parts of potato starch paste of 8 per cent. strength.

A fabric saturated with this stiflening has a hard finish fast to water even when dried at the ordinary temperature.

Example 10 10 parts of the condensation product, made by heating a mixture 01 14.6 parts of 2-chloro-4:6- diamino-1z3z5-triazine, 56 parts by volume of formaldehyde i 32 per cent. strength by volume, 24 parts of ethyl alcohol of 95 per cent. strength and 1 part by volume of concentrated sulfuric acid until a clear solution is obtained, then neutralizing and evaporating to dryness in a vacuum, are dissolved in a mixture of 60 parts by volume of formic acid of 86 per cent. strength and 40 parts by volume of water, and this solution is mixed into a starch paste as described in Example 9.

The stiffening thus obtained produces effects similar to those indicated in Example 9.

Example 11 parts of a condensation product made from 6.35 parts of 2-oxy-4:6-diamino-1z3z5-triazine, 47 parts by volume of formaldehyde of 32 per cent. strength by volume and 2.15 parts by volume 0! concentrated sulfuric acid by heating them together at the boiling point for about 2% hours.

then neutralizing and evaporating the solution obtained, are dissolved in a mixture of 90 parts by volume of formic acid of 86 per cent. strength and 10 parts by volume of water.

2,350,1sa I This solution is mixed with a starch paste as indicated in Example 9. The mixture gives dressing eflects similar to those described in Example 9.

Instead of the condensation products being used in acid or acidified solution as indicated in the foregoing examples, dry preparations may also be used, for example such as are made by intermixture of equal parts of the condensation product anda fixed organic acid such as tartaric acid. Mixtures like these are suitable as commercial products in that they dissolve in water and may b used directly for the various purposes described above, either alone or in admixture with the aforesaid additions, as softeners, stiffening agents, water-proofing agents or the like.

What we claim is:

1. A process for treating textile material, which comprises impregnating the'textile material '51- multaneously with a softening agent consisting of trimethylammonium sulphate of monostearylpara-phenylene diamine and with a creaseproofing agent selected from the group consisting of (l) a hardenable condensation product offormaldehyde and melamine as essential reactants and (2) formaldehyde and melamine in uncondensed form, and then subjecting the impregnated textile material to a temperature between room temperature and about C. until the said crease-proofin agent is converted into the form of an insolubilized formaldehyde-melamine condensation product, whereby anticrease finish which is fast to washing is imparted to the textile material. 1

2. A textile finishing composition suitable for use in the impregnation-of textile material in the imparting of a crease-proof finish thereto, consisting essentially of trimethylammonium sulphate ofmonostearyl-para-phenylenediamine and of a melamine-formaldehyde condensation product, said condensation product being heat hardenable at a temperature between room temperature and about 100 C. whereby'it is insolubilized.

' GUSTAV WHJMER.

WILLI FISCH. 

